CN103123958A - Solid nano porous membrane with temperature sensitive response characteristics and preparation method thereof - Google Patents
Solid nano porous membrane with temperature sensitive response characteristics and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a solid nano porous membrane with temperature sensitive response characteristics and a preparation method thereof. Methacrylic acid benzyl ester with temperature sensitive response characteristics or polymer of derivative of the methacrylic acid benzyl ester is grafted on the solid nano porous membrane serving as a substrate to form the solid nano porous membrane with temperature sensitive response characteristics in a lithium ion battery using ionic liquid as electrolyte. When temperature exceeds lowest critical transformation temperature (120-150 DEG C), in the ionic liquid, of the polymer, the polymer collapses in nano pores of the solid nano porous membrane and on the solid nano porous membrane to block the nano pores, namely the polymer intelligently closes the nano pores to change conductivity of the solid nano porous membrane. In the mean time, the solid nano porous membrane substrate serving as support material is good in stability at high temperature and free of fusing.
Description
Technical field
The invention belongs to the battery diaphragm field in lithium ion battery, have solid nano perforated membrane of temperature sensitive response characteristic and preparation method thereof in particularly take ionic liquid as electrolytical lithium ion battery.
Background technology
Fail safe is the major issue in Study on Li-ion batteries using, because its charge/discharge current is large, radiating condition is poor, causes internal temperature of battery to raise, and occurs sometimes smoldering, the situations such as Fire explosion and even injury to personnel.Barrier film in lithium ion battery can be isolated both positive and negative polarity and be prevented battery short circuit, and the while is as the cut-out electric current of safety device intelligence.Therefore, lithium ion battery separator in use, the safety issue of barrier film is very important.In order to improve the security performance of lithium ion battery, after the temperature in lithium ion battery was raised to a certain degree, the micropore in barrier film should be able to be closed, makes the electrode cessation reaction.Barrier film requires to have high porosity (＞45%), high security and high thermal stability as barrier film.The fail safe of barrier film and thermal stability are to be determined by the character of barrier film itself, depend primarily on its blocking temperature and two values of break temperature.The blocking temperature of barrier film refers to that the barrier film of loose structure at a certain temperature fusing occurs causes microcellular structure to be closed, internal resistance increase sharply and block electric current by the time temperature.The blocking temperature is too low, and namely the barrier film starting point of closing is too low, can affect the normal performance of battery performance; The blocking excess Temperature can not in time suppress the danger of the rapid heat production of battery.The break temperature of barrier film is higher than the blocking temperature, and barrier film meeting this moment failure, fusing cause both positive and negative polarity directly to contact.Consider from the battery security angle, the blocking temperature of barrier film should have a wider scope, and this moment, barrier film can not destroy.Existing battery diaphragm material mainly contains the PE of individual layer and PP film, compound PP-PE-PP film and compound multilayer film (CN1062357, CN1034357, CN1296195, CN101343374A).Poly blocking temperature is at 120-130 ℃, and polyacrylic blocking temperature is at 150-160 ℃, and the adjusting temperature of both composite membranes is at 130-140 ℃, the narrow range of adjusting; And after the temperature in lithium ion battery further was increased to 160-170 ℃, this barrier film will fuse, and causes danger.
For the safety of lithium ion battery, need to develop a kind of brand-new intelligent battery barrier film, at high temperature plug-hole automatically, cut off electric current, and the structure of itself is not destroyed simultaneously, prevents interelectrode contact.
Summary of the invention
The object of the present invention is to provide a kind of solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film, have the performance of closing the duct in temperature is 120-150 ℃ of scope.
Another object of the present invention is to be provided as the preparation method of the solid nano perforated membrane with temperature sensitive response characteristic of lithium ion battery intelligence barrier film.
The solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film of the present invention, by in the surperficial Atom Transfer Radical Polymerization reaction as the solid nano perforated membrane of substrate, i.e. method by chemical bonding, has the polymer of the methacrylic acid benzyl ester or derivatives thereof of temperature sensitive response characteristic on as the solid nano perforated membrane of substrate in grafting, the solid nano perforated membrane that has the temperature sensitive response characteristic in being formed on take ionic liquid as electrolytical lithium ion battery.
the described solid nano perforated membrane that has the temperature sensitive response characteristic in take ionic liquid as electrolytical lithium ion battery, when temperature is 120-150 ℃, the minimum critical transition temperature (120-150 ℃) of polymer in ionic liquid that surpasses described methacrylic acid benzyl ester or derivatives thereof when temperature, the state of polymer in electrolyte of described methacrylic acid benzyl ester or derivatives thereof can change, will collapse in the nano pore of described solid nano perforated membrane as substrate and on film, block described nano pore, namely this polymer is closed the nano pore as the solid nano perforated membrane of substrate intelligently, change is as the conductivity of the solid nano perforated membrane of substrate.
The polymer of described methacrylic acid benzyl ester or derivatives thereof has the temperature sensitive response characteristic in temperature is 120-150 ℃ of scope, its structure is:
Wherein:
M is the natural number of 1-10.
When described electrolytical temperature is 120-150 ℃; be grafted on as the polymer of the methacrylic acid benzyl ester or derivatives thereof with temperature sensitive response characteristic on the solid nano perforated membrane of substrate and will and collapse on film in the nano pore of described solid nano perforated membrane as substrate; block described nano pore; cut off electric current, the protection cell circuit.
Described electrolyte is 1,3 two (trifluoromethyl sulfonyl) imines classes of the imidazoline that replaces preferably.
Described solid nano perforated membrane with temperature sensitive response characteristic is to have the temperature sensitive response characteristic under 120-150 ℃ in temperature.
Described solid nano perforated membrane with temperature sensitive response characteristic is under 120-150 ℃ in temperature, its conductivity is the 1/6-1/8 of the conductivity of described solid nano perforated membrane as substrate, after being the polymer of grafting methacrylic acid benzyl ester or derivatives thereof, conductivity as the solid nano perforated membrane of substrate has descended 6-8 doubly, effectively blocked electric current, prevented that the temperature of inside lithium ion cell from further raising.
Described solid nano perforated membrane with temperature sensitive response characteristic is under 120-150 ℃ in temperature, and its porosity is 10-20%.
The porosity of described solid nano perforated membrane as substrate is 50%-70%.
The aperture of described nano pore is 20-200nm.
Described thickness with solid nano perforated membrane of temperature sensitive response characteristic is 10-60 μ m.
Described solid nano perforated membrane as substrate be commercialization or can homemade mineral-type or the solid nano perforated membrane of organic in a kind of.
The thickness of the solid nano perforated membrane of described mineral-type is 10-60 μ m, is selected from a kind of in the solid nano perforated membrane of anodised aluminium, mica, silicon, silicon dioxide and silicon nitride; The thickness of the solid nano perforated membrane of described organic is 10-60 μ m, is selected from a kind of in the nano-porous films of PETG, polyimide film and Merlon.
The preparation method of the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film of the present invention mainly comprises the following steps:
1). choose contain hydroxyl in the treated surface that obtains the solid nano perforated membrane as substrate, clean dried for standby;
2). with step 1) the solid nano perforated membrane that obtains after drying is immersed in the methanol solution that contains 1wt%-4wt%3-(trimethoxysilyl)-1-propylamine and reacts (time of general reaction is 10-18 hour), taking-up and clean oven dry with methyl alcohol or with carrene after reaction is completed;
3). with step 2) the solid nano perforated membrane that obtains is immersed in the dichloromethane solution that contains the 2wt% pyridine after oven dry, when being 0 ℃, temperature add the initator of acylbromide class to react, approximately reaction is about 1 hour, and wherein the molar ratio of the initator of acylbromide class and monomer methacrylic acid benzyl ester or derivatives thereof is 1/100-3/100; Then at room temperature continue reaction, the general time of continuing again reaction is 10-14 hour again, takes out film and cleans oven dry with carrene;
4). add in reactor toluene solvant, then monomer methacrylic acid benzyl ester or derivatives thereof is joined (the monomer methacrylic acid benzyl ester or derivatives thereof that generally adds 10vol%-30vol%) in this reactor, pass into the air in inert gas (as nitrogen) eliminating reactor; Add the catalyst cuprous bromide: the mol ratio of pentamethyl-diethylenetriamine is cuprous bromide and the pentamethyl-diethylenetriamine of 1: 3, obtain mixed liquor, wherein, catalyst cuprous bromide: the molar ratio of monomer methacrylic acid benzyl ester or derivatives thereof is 1/200-1/600; Then with step 3) the solid nano perforated membrane that is grafted with the acylbromide quasi-molecule that obtains is immersed in above-mentioned mixed liquor after oven dry, be reaction under 85-95 ℃ in temperature, general about reaction 2-12 hour, obtain the polymer of methacrylic acid benzyl ester or derivatives thereof on the surface as the solid nano perforated membrane of substrate, obtain the described solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery separator.
Described acylbromide class initator: for example α-bromine isobutyl acylbromide or 2,4-dichloro-benzoyl MB.
The solid nano perforated membrane that hydroxyl is contained on the described treated surface that obtains is selected from a kind of in the solid nano perforated membrane of PETG, polyimide film, Merlon, anodised aluminium, mica, silicon, silicon dioxide and silicon nitride.
The method that the solid nano perforated membrane of hydroxyl is contained on the described treated surface that obtains comprises Physical and chemical method: anodised aluminium as described, silicon or silica solid nano-porous films can obtain containing the solid nano perforated membrane of hydroxyl by the method for oxygen plasma bombarded surface.Described PETG, polyimide film, Merlon, mica or silicon nitride solid nano perforated membrane can by the method for chemical corrosion, as soaking with the strong sodium hydroxide solution of highly basic, can obtain containing the solid nano perforated membrane of hydroxyl.
Described methacrylic acid benzyl ester or derivatives thereof monomer is commercial prod, and its structure is:
Wherein:
M is the natural number of 1-10
In the present invention, no longer continue to use traditional PE, PP and composite membrane thereof, but select solid inorganic class or organic solid nano perforated membrane as backing material, introduce the polymer of intelligent temperature response on described solid inorganic class or organic solid nano perforated membrane with the method for chemical bonding, the responsive response temperature of this polymer can be regulated in 120-150 ℃ of scope, when temperature surpasses 120-150 ℃, polymer will be collapsed in the nano pore of solid inorganic class or organic solid nano perforated membrane He on film, blocks nano pore; The Heat stability is good of the material of while solid inorganic class or organic solid nano perforated membrane, this depends on the character of solid inorganic class or organic solid nano perforated membrane itself, even general still stable in the time of 200 ℃, can prevent that like this solid nano perforated membrane with temperature sensitive response characteristic of the present invention from fusing, dissolving when high temperature, stop the both positive and negative polarity contact, guaranteed the safety of lithium ion battery.
Description of drawings
Fig. 1. of the present invention in the nano pore of solid nano perforated membrane and the route map of the polymer of the surface grafting methacrylic acid benzyl ester of film or derivative.
Fig. 2. the operation principle with solid nano perforated membrane of temperature sensitive response characteristic of the present invention, LCST refers to minimum critical transition temperature.When the temperature take ionic liquid as electrolytical electrolyte ion liquid during higher than the minimum critical transition temperature of polymer of methacrylic acid benzyl ester or derivatives thereof, described polymer will be collapsed on the nano pore of the solid nano perforated membrane with temperature sensitive response characteristic and film, block described nano pore, so the electrolyte ion liquid-liquid can not be passed through described nano pore.
Fig. 3. the Electronic Speculum figure of the anodised aluminium nano-porous films (aperture of nano pore is 100nm) that the embodiment of the present invention 1 is used, porosity is 67%.
Fig. 4. have the Electronic Speculum figure of the anodised aluminium nano-porous films with temperature sensitive response characteristic after the polymethylacrylic acid benzyl ester of temperature sensitive response characteristic in the grafting of the embodiment of the present invention 1.
Fig. 5. the atomic force scintigram of the anodised aluminium nano-porous films that the embodiment of the present invention 1 is used, sweep limits are 2 μ m * 2 μ m.
Fig. 6. have the atomic force scintigram that has the anodised aluminium nano-porous films of temperature sensitive response characteristic after the polymethylacrylic acid benzyl ester of temperature sensitive response characteristic in the grafting of the embodiment of the present invention 1, sweep limits is 2 μ m * 2 μ m.
Embodiment
Embodiment 1
See also Fig. 1 and Fig. 2, the anodised aluminium nano-porous films that preparation has the temperature sensitive response characteristic.
1). the surface treatment of anodised aluminium nano-porous films
(aperture of nano pore is 100nm with clear water and ethanol anode purge aluminium oxide nano perforated membrane, porosity is 67%, Electronic Speculum figure as shown in Figure 3, the atomic force scintigram as shown in Figure 5), then put into concentration and be 5% watery hydrochloric acid, anode purge aluminium oxide nano perforated membrane 20-30 second under room temperature, then water is clean with the surface washing of anodised aluminium nano-porous films, the anodised aluminium nano-porous films is put into distilled water 3-4 hour, taking-up is dried stand-by again.
With clean and dry after the anodised aluminium nano-porous films be placed in oxygen plasma, when power is 200W, with the surface of oxygen plasma bombardment anodised aluminium nano-porous films 5 minutes, then that film is dry, obtain the anodised aluminium nano-porous films that free hydroxyl is contained on the surface.
2). the surface grafting initator
With step 1) the anodised aluminium nano-porous films that obtains after drying is immersed in the methanol solution (10mL) that contains 2wt%3-(trimethoxysilyl)-1-propylamine and reacted 10 hours, take out and clean oven dry with methyl alcohol or chloromethanes;
Then the anodised aluminium nano-porous films that will obtain after drying is immersed in the dichloromethane solution (10mL) that contains the 2wt% pyridine, when being 0 ℃, temperature add the α of 20 μ L-bromine isobutyl acylbromide to react 1 hour, at room temperature continue again reaction 12 hours, take out film and clean oven dry with carrene;
3). polymerization reaction
add in reactor 10mL to toluene solvant, then add 1g methacrylic acid benzyl ester, pass into nitrogen and get rid of air in reactor half an hour, the pentamethyl-diethylenetriamine that adds 25 μ mol cuprous bromides and 75 μ mol, obtain mixed liquor, then with step 3) the anodised aluminium nano-porous films that is grafted with α-bromine isobutyryl molecular bromine that obtains is immersed in above-mentioned mixed liquor after oven dry, be 90 ℃ of lower polymerization reactions 6 hours in temperature, obtain the polymethylacrylic acid benzyl ester on the surface as the anodised aluminium nano-porous films of substrate, this polymethylacrylic acid benzyl ester is that the mode with chemical bonding is grafted on the surface as the anodised aluminium nano-porous films of substrate, obtain take ionic liquid as the electrolytical anodised aluminium nano-porous films with temperature sensitive response characteristic as lithium ion battery separator.Electronic Speculum figure as shown in Figure 4, the atomic force scintigram is as shown in Figure 6.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 120 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/8.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 16%.
The structure of described methacrylic acid benzyl ester monomer is:
Embodiment 2
Substantially with embodiment 1, difference is the preparation method, step 3) polymerization reaction in what add is the monomer methacrylic acid benzyl ester of 2g.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 140 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte (table 1), described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/7.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 18%.
Substantially with embodiment 1, difference is the preparation method, step 3) polymerization reaction in what add is the monomer of 3g.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 151 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/6.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 20%.
Embodiment 4
The preparation method is substantially with embodiment 1, and difference is, what select is that the aperture of nano pore is the Electrochemical anodization of 20nm.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 130 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/8.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 19%.
Embodiment 5
The preparation method is substantially with embodiment 1, and difference is, what select is that the aperture of nano pore is the Electrochemical anodization of 80nm.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 145 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/6.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 10%.
Embodiment 6
Substantially with embodiment 1, difference is the preparation method, step 3) polymerization time be 2 hours.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 150 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/8.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 20%.
Embodiment 7
Substantially with embodiment 1, difference is the preparation method, step 3) polymerization time be 12 hours.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 140 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/7.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 12%.
Embodiment 8
The preparation method is substantially with embodiment 1, and difference is, with step 2) in the anodised aluminium nano-porous films be immersed in the reaction of carrying out in the methanol solution that contains 4wt%3-(trimethoxysilyl)-1-propylamine.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 130 ℃ of the minimum critical transition temperature of described polymethylacrylic acid benzyl ester in above-mentioned electrolyte, described polymethylacrylic acid benzyl ester will be collapsed in the nano pore of described anodised aluminium nano-porous films as substrate and on film, block described nano pore, change the conductivity as the anodised aluminium nano-porous films of substrate; Its conductivity be described anodised aluminium nano-porous films as substrate conductivity 1/6.
Porosity with anodised aluminium nano-porous films of temperature sensitive response characteristic is 15%.
Embodiment 9
1). the processing of nanoporous silicon fiml
Nanoporous silicon fiml (aperture of nano pore is 100nm) with ethanol and isopropyl alcohol soaking and washing, is then cleaned with clear water, dry stand-by.
With clean and dry after the nanoporous silicon fiml be placed in oxygen plasma, then that film is dry with the surface of oxygen plasma bombardment nanoporous silicon fiml 5 minutes when power is 200W, obtain the nanoporous silicon fiml that free hydroxyl is contained on the surface.
2) then according to the step 2 of embodiment 1)-3) technical scheme continue the nanoporous silicon fiml that preparation has the temperature sensitive response characteristic, difference is that the monomer of use is the 2-methacrylic acid phenethyl ester of 2g, structure is as follows:
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-ethyl-3-methylimidazole quinoline, when temperature surpasses 123 ℃ of the minimum critical transition temperature of described poly-2-methacrylic acid phenethyl ester in above-mentioned electrolyte, described poly-2-methacrylic acid phenethyl ester will be collapsed in the nano pore of described nanoporous silicon fiml as substrate and on film, block described nano pore, change the conductivity as the nanoporous silicon fiml of substrate; Its conductivity be described nanoporous silicon fiml as substrate conductivity 2/15.
Porosity with nanoporous silicon fiml of temperature sensitive response characteristic is 16%.
Embodiment 10
1). the processing of nanoporous PETG (PET) film
The sodium hydrate aqueous solution of nanoporous PETG film with 1mol/L soaked 2 minutes, clean, soaked 1 hour with clear water, then dry, obtain the nanoporous PET film that free hydroxyl is contained on the surface.
2) then continue according to the technical scheme of embodiment 9 the nanoporous PET film that preparation has the temperature sensitive response characteristic.
In two (trifluoromethyl sulfonyl) imines of electrolyte 1-propyl group-3-methylimidazole quinoline, when temperature surpasses 130 ℃ of the minimum critical transition temperature of described poly-2-methacrylic acid phenethyl ester in above-mentioned electrolyte, described poly-2-methacrylic acid phenethyl ester will be collapsed in the nano pore of described nanoporous PETG (PET) film as substrate and on film, block described nano pore, change the conductivity as nanoporous PETG (PET) film of substrate; Its conductivity be described nanoporous PETG (PET) film as substrate conductivity 1/7.
Porosity with nanoporous PETG film of temperature sensitive response characteristic is 18%.
The barrier film blocking temperature of table 1. embodiment 1-7
Claims (10)
1. solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film, it is characterized in that: be grafted with the polymer of the methacrylic acid benzyl ester or derivatives thereof with temperature sensitive response characteristic on the solid nano perforated membrane as substrate, the solid nano perforated membrane that has the temperature sensitive response characteristic in being formed on take ionic liquid as electrolytical lithium ion battery;
When described electrolytical temperature is 120-150 ℃, is grafted on as the polymer of the methacrylic acid benzyl ester or derivatives thereof with temperature sensitive response characteristic on the solid nano perforated membrane of substrate and will and collapses on film in the nano pore of described solid nano perforated membrane as substrate;
Described solid nano perforated membrane as substrate is a kind of in inorganic or organic solid nano perforated membrane.
2. the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film according to claim 1, it is characterized in that: the described solid nano perforated membrane that has the temperature sensitive response characteristic in take ionic liquid as electrolytical lithium ion battery, during the minimum critical transition temperature of the polymer that surpasses described methacrylic acid benzyl ester or derivatives thereof when temperature in ionic liquid, the polymer of described methacrylic acid benzyl ester or derivatives thereof will be collapsed in the nano pore of described solid nano perforated membrane as substrate and on film, block described nano pore, change is as the conductivity of the solid nano perforated membrane of substrate,
The polymer of described methacrylic acid benzyl ester or derivatives thereof has the temperature sensitive response characteristic in temperature is 120-150 ℃ of scope, its structure is:
Wherein:
M is the natural number of 1-10.
3. the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film according to claim 1 and 2, it is characterized in that: described solid nano perforated membrane with temperature sensitive response characteristic is under 120-150 ℃ in temperature, and its conductivity is the 1/6-1/8 of the conductivity of described solid nano perforated membrane as substrate.
4. the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film according to claim 3, it is characterized in that: described solid nano perforated membrane with temperature sensitive response characteristic is under 120-150 ℃ in temperature, and its porosity is 10-20%;
The porosity of described solid nano perforated membrane as substrate is 50%-70%.
5. the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film according to claim 1 and 2, it is characterized in that: the aperture of described nano pore is 20-200nm.
6. the solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film according to claim 1, it is characterized in that: the thickness of described inorganic solid nano perforated membrane is 10-60 μ m, is selected from a kind of in the solid nano perforated membrane of anodised aluminium, mica, silicon, silicon dioxide and silicon nitride; The thickness of described organic solid nano perforated membrane is 10-60 μ m, is selected from a kind of in the nano-porous films of PETG, polyimide film and Merlon.
7. the preparation method of the described solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery intelligence barrier film of an any one, it is characterized in that: this preparation method comprises the following steps:
1). choose contain hydroxyl in the treated surface that obtains the solid nano perforated membrane as substrate, clean dried for standby;
2). with step 1) the solid nano perforated membrane that obtains after drying is immersed in the methanol solution that contains 1wt%-4wt%3-(trimethoxysilyl)-1-propylamine and reacts, taking-up and clean oven dry with methyl alcohol or with carrene after reaction is completed;
3). with step 2) the solid nano perforated membrane that obtains is immersed in the dichloromethane solution that contains the 2wt% pyridine after oven dry, add the initator of acylbromide class to react when temperature is 0 ℃, wherein the molar ratio of the initator of acylbromide class and monomer methacrylic acid benzyl ester or derivatives thereof is 1/100-3/100; Then at room temperature continue again reaction 10-14 hour, take out film and clean oven dry with carrene;
4). add in reactor toluene solvant, then monomer methacrylic acid benzyl ester or derivatives thereof is joined in this reactor, pass into the air in inert gas eliminating reactor; Add the catalyst cuprous bromide: the mol ratio of pentamethyl-diethylenetriamine is cuprous bromide and the pentamethyl-diethylenetriamine of 1: 3, obtain mixed liquor, wherein, catalyst cuprous bromide: the molar ratio of monomer methacrylic acid benzyl ester or derivatives thereof is 1/200-1/600; Then with step 3) the solid nano perforated membrane that is grafted with the acylbromide quasi-molecule that obtains is immersed in above-mentioned mixed liquor after oven dry, be to react under 85-95 ℃ in temperature, obtain the polymer of methacrylic acid benzyl ester or derivatives thereof on the surface as the solid nano perforated membrane of substrate, obtain the described solid nano perforated membrane with temperature sensitive response characteristic as lithium ion battery separator.
8. preparation method according to claim 7, it is characterized in that: described acylbromide class initator is α-bromine isobutyl acylbromide or 2,4-dichloro-benzoyl MB.
9. preparation method according to claim 7, it is characterized in that: its structure of described methacrylic acid benzyl ester or derivatives thereof monomer is:
10. preparation method according to claim 7 is characterized in that: the solid nano perforated membrane that hydroxyl is contained on the described treated surface that obtains is selected from a kind of in the solid nano perforated membrane of PETG, polyimide film, Merlon, anodised aluminium, mica, silicon, silicon dioxide and silicon nitride.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151599A (en) * | 2014-07-18 | 2014-11-19 | 复旦大学 | Ionic liquid functionalized temperature-responsive composite film and preparation method thereof |
| CN107163282A (en) * | 2017-07-19 | 2017-09-15 | 中国科学院长春应用化学研究所 | Macroporous polymer resin of fast temperature response and preparation method thereof |
| CN107759726A (en) * | 2017-09-18 | 2018-03-06 | 中山大学 | A kind of responsive to temperature type polymer dielectric and its preparation method and application |
| CN109455662A (en) * | 2018-11-26 | 2019-03-12 | 广东工业大学 | A kind of New Solid nano-pore structure |
| CN110229370A (en) * | 2018-03-07 | 2019-09-13 | 中天电子材料有限公司 | The modified method in Kapton surface and Kapton |
| US10693188B2 (en) | 2014-10-30 | 2020-06-23 | Clemson University | Thermally responsive electrolytes |
| US11325076B2 (en) | 2018-08-13 | 2022-05-10 | National Taiwan University | Battery having separator including mesoporous silica thin film positioned on macroporous substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101343374A (en) * | 2008-08-18 | 2009-01-14 | 中国科学院化学研究所 | Polypropylene porous membrane with temperature sensitivity and preparation thereof |
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2011
- 2011-11-17 CN CN201110366945.1A patent/CN103123958B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343374A (en) * | 2008-08-18 | 2009-01-14 | 中国科学院化学研究所 | Polypropylene porous membrane with temperature sensitivity and preparation thereof |
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| TAKESHI UEKI等: "Lower critical solution temperature behavior of linear polymers in ionic liquids and the corresponding volume phase transition of polymer gels", 《LANGMUIR》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151599A (en) * | 2014-07-18 | 2014-11-19 | 复旦大学 | Ionic liquid functionalized temperature-responsive composite film and preparation method thereof |
| CN104151599B (en) * | 2014-07-18 | 2017-02-15 | 复旦大学 | Ionic liquid functionalized temperature-responsive composite film and preparation method thereof |
| US10693188B2 (en) | 2014-10-30 | 2020-06-23 | Clemson University | Thermally responsive electrolytes |
| CN107163282A (en) * | 2017-07-19 | 2017-09-15 | 中国科学院长春应用化学研究所 | Macroporous polymer resin of fast temperature response and preparation method thereof |
| CN107759726A (en) * | 2017-09-18 | 2018-03-06 | 中山大学 | A kind of responsive to temperature type polymer dielectric and its preparation method and application |
| CN110229370A (en) * | 2018-03-07 | 2019-09-13 | 中天电子材料有限公司 | The modified method in Kapton surface and Kapton |
| US11325076B2 (en) | 2018-08-13 | 2022-05-10 | National Taiwan University | Battery having separator including mesoporous silica thin film positioned on macroporous substrate |
| CN109455662A (en) * | 2018-11-26 | 2019-03-12 | 广东工业大学 | A kind of New Solid nano-pore structure |
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|---|---|
| CN103123958B (en) | 2015-03-11 |
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